ALLEN Chemical Kinetics 1

5. For an elementary chemical reaction,

CHEMICAL KINETICS
ˆˆˆ† k1 d[A]
1. Decomposition of X exhibits a rate constant of A2 ‡ˆˆ ˆ 2A, the expression for is :
k –1
dt
0.05 mg/year. How many years are required for
(1) 2k1[A2]–k–1[A]2
the decomposition of 5 mg of X into 2.5 mg ? (2) k1[A2]–k–1[A]2
(1) 50 (2) 25 (3) 2k1[A2]–2k–1[A]2
(3) 20 (4) 40 (4) k1[A2]+k–1[A]2
6. For the reaction, 2A + B ® products, when the
2. If a reaction follows the Arrhenius equation,
concentrations of A and B both wrere doubled,
1 the rate of the reaction increased from 0.3 mol
the plot lnk vs gives straight line with a
(RT) L –1 s –1 to 2.4 mol L –l s –1 . When the
gradient (–y) unit. The energy required to concentration of A alone is doubled, the rate
activate the reactant is : increased from 0.3 mol L–1s–1 to0.6 mol L–1s–1
Which one of the following statements is
(1) y unit (2) –y unit

3.
(3) yR unit

EN (4) y/R unit

The reaction 2X ® B is a zeroth order
reaction. If the initial concentration of X is
0.2 M, the half-life is 6 h. When the initial
concentration of X is 0.5 M, the time required
to reach its final concentration of 0.2 M will
7.
correct ?
(1) Order of the reaction with respect to Bis2
(2) Order of the reaction with respect to Ais2
(3) Total order of the reaction is 4
(4) Order of the reaction with respect to B is 1
For a reaction, consider the plot of ln k versus
1/T given in the figure. If the rate constant of
this reaction at 400 K is 10–5 s–1, then the rate
be :-
constant at 500 K is :
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(1) 18.0 h (2) 7.2 h
(3) 9.0 h (4) 12.0 h
ln k slope = –4606K
4. Consider the given plots for a reaction obeying
Arrhenius equation (0°C < T < 300°C) :
(k and E a are rate constant and activation 1/T
energy, respectively) (1) 2×10–4 s–1 (2) 10–4 s–1
A

(3) 10–6 s–1 (4) 4×10–4 s–1

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8. The following results were obtained during

k k kinetic studies of the reaction :
2A + B ® Products
Ea T(°C) Experment [A] [B] Initial Rate of reaction
I II (in mol L -1) (in mol L-1 ) (in mol L–1 min–1)

(I) 0.10 0.20 6.93 × 10–3

Choose the correct option : (II) 0.10 0.25 6.93 × 10–3

(1) Both I and II are wrong (III) 0.20 0.30 1.386 × 10–2

(2) I is wrong but II is right

The time (in minutes) required to consume half
(3) Both I and II are correct
of A is :
(4) I is right but II is wrong
(1) 10 (2) 5 (3) 100 (4) 1
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2 Chemical Kinetics ALLEN
9. For the reaction 2A +B ® C, the values of 12. For the reaction of H2 with I2, the rate constant is
initial rate at different reactant concentrations 2.5×10–4dm3 mol–1 s–1 at 327°C and 1.0 dm 3
are given in the table below. The rate law for
mol –1 s –1 at 527°C. The activation energy
the reaction is :
for the reaction, in kJ mol –1 is:
[A] (mol L–1) [B] (mol L–1) Initial Rate
(mol L–1s–1) (R=8.314J K–1 mol–1)
0.05 0.05 0.045 (1) 72 (2) 166 (3) 150 (4) 59
0.10 0.05 0.090 13. In the following reaction; xA ® yB
0.20 0.10 0.72
é d[A] ù é d[B] ù
(1) Rate = k [A][B] log10 ê - ú = log10 ê ú + 0.3010
ë dt û ë dt û
(2) Rate = k [A]2[B]2
'A' and 'B' respectively can be :
(3) Rate = k [A][B]2
(1) n-Butane and Iso-butane
(4) Rate = k [A]2[B]
(2) C2H4 and C4H8
k1 k2
10. For a reaction scheme A ¾¾ ® B ¾¾ ® C , if (3) N2O4 and NO2
the rate of formation of B is set to be zero then (4) C2H2 and C6H6

11.
æ k1 ö
(1) ç k ÷ [A]
è 2ø
(3) k1k2[A]
EN
the concentration of B is given by :

(2) (k1 + k2) [A]

(4) (k1 – k2) [A]

The given plots represent the variation of the
concentration of a reactant R with time for two
14. NO2 required for a reaction is produced by the
decomposition of N2O5 in CCl4 as per the
equation
2N2O5(g) ® 4NO2(g) + O2(g).
The initial concentration of N2O5 is 3.00 mol L–1
and it is 2.75 mol L–1 after 30 minutes. The rate
different reactions (i) and (ii). The respective of formation of NO2 is :
orders of the reactions are :
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(1) 2.083 × 10–3 mol L–1 min–1
(2) 4.167 × 10–3 mol L–1 min–1
(3) 8.333 × 10–3 mol L–1 min–1
(4) 1.667 × 10–2 mol L–1 min–1
(1) 1,0 (2) 1,1 (3) 0,1 (4) 0,2
A

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 ALLEN Chemical Kinetics 3

SOLUTION 8. Ans. (2)

1. Ans.(1) 6.93 × 10–3 = K × (0.1)x (0.2)y
Rate constant (K) = 0.05 µg/year 6.93 × 10–3 = K × (0.1)x (0.25)y
means zero order reaction So y = 0
a0 5µg and 1.386 × 10–2 = K × (0.2)x (0.30)y
t1/ 2 = =
2K 2 ´ 0.05 mg / year = 50 year x
1 æ1ö
2. Ans. (1) =ç ÷ x =1
2 è2ø
3. Ans. (1)
For zero order So r = K × (0.1) × (0.2)0
[A0]–[At] = kt 6.93 × 10–3 = K × 0.1 × (0.2)0
0.2 – 0.1 = k×6 K = 6.93 ´10-2
1
k= M/hr 0.693 0.693 10
60 t1/ 2 = = -1 = =5
2K 0.693 ´ 10 ´ 2 2
1
and 0.5–0.2 = ´t 9. Ans.(3)
60
Sol. r = K [A]x [B]y
4.
t = 18 hrs.
Ans. (4)
EN
On increasing Ea, k decreases.
In plot II initially k is shown to be almost
constant with temperature while as in moderate
temperature range increase of k is very sharp,
therefore plot II is incorrect.
0.045 = K (0.05)x (0.05)y
0.090 = K (0.10)x (0.05)y
0.72 = K (0.20)x (0.10)y

From (1) ¸ (2),

0.045 æ 0.05 ö
=ç ÷ Þ x =1
0.090 è 0.10 ø
x
x
....(1)
....(2)
....(3)

y
0.090 æ 0.10 ö æ 0.05 ö
5. Ans. (3) From (2) ¸ (3), =ç ÷ ·ç ÷ Þ y=2
0.720 è 0.20 ø è 0.10 ø
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Ans.(3)
Hence, r = K [A] [B]2
ˆˆˆˆ
†
A 2 ‡ˆˆˆ
K1
ˆ 2A Correct option : (3)
K –1
10. Ans.(1)
d[A] K1
Sol. A ¾¾ K2
® B ¾¾® C
= 2k1[A 2 ] - 2k –1[A]2
dt
d[B]
6. Ans. (1) = 0 = K1[A] - K 2 [B]
dt
A

x y
r = K[A] [B] K1
Þ [B] = K [A]
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Þ8=2 =2
3 x+y
2
Þ x + y = 3 ...(1) 11. Ans.(1)
Þ2=2
x
Sol. (i) ln[R] = ln[R]0 – Kt (Ist order)
Þ x = 1, y = 2 [R] = [R]0 – Kt (zero order)
Order w.r.t. A = 1 \ Ans.(1)
Order w.r.t. B = 2
7. Ans.(2)
K2 Ea é 1 1 ù
ln = ê - ú
K1 R ë T1 T2 û

K2 é 1 1 ù
2.303log -5
= 4606 ê - úû
10 ë 400 500
Þ K2 = 10–4 s-1
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4 Chemical Kinetics ALLEN
12. Ans.(2) 14. Ans.(4)
Sol. H2(g) + I2(g) ® 2HI(g) Sol. 2N2O5(g) ¾® 4NO2(g) + O2(g)
Apply Arrhenius equation t=0 3.0M
K2 Ea æ 1 1 ö t=30 2.75 M
log = ç - ÷
K1 2.303R è 600 800 ø -D [ N 2 O5 ] 0.25
=
1 Ea æ 200 ö Dt 30
log = ç ÷
2.5 ´ 10 -4
2.303 ´ 8.31 è 600 ´ 800 ø 1 -D [ N2 O5 ] 1 D [ NO2 ]
´ = ´
\ Ea » 166kJ/mol 2 Dt 4 Dt
13. Ans.(2) D [ NO2 ] 0.25
= ´ 2 = 1.66 × 10–2 M/min
- d[A] d[B] Dt 30
Sol. log = log + 0.3010
dt dt
- d[A] d[B]
= 2´
dt dt
1 -d[A] d[B]
´ =
2 dt
2A —® B
2C2H4 —® C4H8 EN
dt
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A

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